KR20010016592A - Preparation Method of the Functional Polymeric Beads by Radiation-induced Polymerization and Its Functional Polymeric Beads - Google Patents

Preparation Method of the Functional Polymeric Beads by Radiation-induced Polymerization and Its Functional Polymeric Beads Download PDF

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KR20010016592A
KR20010016592A KR1020000081429A KR20000081429A KR20010016592A KR 20010016592 A KR20010016592 A KR 20010016592A KR 1020000081429 A KR1020000081429 A KR 1020000081429A KR 20000081429 A KR20000081429 A KR 20000081429A KR 20010016592 A KR20010016592 A KR 20010016592A
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radiation
polymer beads
functional polymer
functional
beads
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최성호
이광필
서재완
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이광필
최성호
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

PURPOSE: Provided is a process for producing functional polymer beads by a radiation polymerization, the functional polymer beads can be used as functional biomaterial and material of an affinity column for separating protein. CONSTITUTION: The functional polymer beads are produced by dissolving a mixed vinyl based monomer having functional groups in an organic solvent and performing the polymerization by irradiating the radiation to produce the functional polymer beads and then filtering and drying the produced beads. The mixed vinyl based monomer is at least one selected from the group consisting of diethyleneglycol dimethacrylate, glycidyl methacrylate, methacryloyl chloride, and acryloyl chloride.

Description

방사선 중합법에 의한 기능성 고분자 비드의 제조 방법 및 그 기능성 고분자 비드 {Preparation Method of the Functional Polymeric Beads by Radiation-induced Polymerization and Its Functional Polymeric Beads}Preparation Method of Functional Polymer Beads by Radiation Polymerization Method and Functional Polymer Beads {Preparation Method of the Functional Polymeric Beads by Radiation-induced Polymerization and Its Functional Polymeric Beads}

본 발명은 새로운 기능성 바이오 재료 및 크로마토그래피 칼럼 재료로 이용할 수 있는 방사선 중합법에 의한 기능성 고분자 비드를 제조하는데 그 목적이 있다.The present invention aims to produce functional polymer beads by radiation polymerization which can be used as novel functional biomaterials and chromatography column materials.

본 발명은 의약용 기능성 바이오 재료, 신약개발에 있어 조합화학에 사용되는 비드(bead), 단백질 분리용 아피니티(affinity) 칼럼 재료 등에 다양하게 응용할 수 있는 방사선 중합법에 의한 기능성 고분자 비드의 제조방법 및 그 기능성 고분자 비드에 관한 것이다.The present invention provides a method for producing functional polymer beads by radiation polymerization which can be applied to various functional biomaterials for medical use, beads used in combinatorial chemistry in developing new drugs, and affinity column materials for protein separation. And functional polymer beads thereof.

방사선 그래프트 중합법 (Radiation-induced graft polymerization)이란 일반적으로 고분자 재료에 방사선을 조사하여 고분자 내에 존재하는 탄소-수소의 결합을 끊어 라디칼을 생성시키고, 이 라디칼을 개시제로 하여 다양한 기능을 갖은 단량체를 도입하여 새로운 고기능성 고분자 재료를 제조하는 방법이다.Radiation-induced graft polymerization generally involves irradiating a polymer material with radiation to break the carbon-hydrogen bonds present in the polymer to generate radicals, and introduce radicals with various functions using this radical as an initiator. To produce a new high-functional polymer material.

대한민국 특허 (출원번호:10-2000-49939호)는 방사선 그래프트를 이용한 고분자 형광체의 제조방법 및 그 고분자 형광체에 대하여 나타내고 있다. 이 발명에는 기존의 고분자 재료를 방사선 그래프트를 이용하여 고분자 형광체를 제조하는 방법에 대하여 자세히 언급되어 있다.Korean Patent Application (Application No.:10-2000-49939) discloses a method for producing a polymeric fluorescent substance using a radiation graft and a polymeric fluorescent substance thereof. In the present invention, a method for producing a polymer phosphor using a radiation graft of an existing polymer material is mentioned in detail.

한편, 방사선 중합법 (Radiation-induced Polymerization)이란, 비닐계 단 량체를 유기용매에 용해시켜 방사선을 조사하여 방사선에 의해 발생하는 라디칼을 이용하여 고분자를 제조하는 방법이다.On the other hand, radiation-induced polymerization is a method of producing a polymer using a radical generated by radiation by dissolving a vinyl monomer in an organic solvent to irradiate radiation.

..

도 1 : 본 발명의 기능성 고분자 비드의 SEM 분석도로,1: SEM analysis of the functional polymer beads of the present invention,

(a) 수용액에서 얻어진 기능성 고분자 비드, (b) 메탄올에서 얻어진 기능성고분자 비드, (c) 에탄올에서 얻어진 기능성 고분자 비드,(a) functional polymer beads obtained in aqueous solution, (b) functional polymer beads obtained in methanol, (c) functional polymer beads obtained in ethanol,

(d) 톨루엔에서 얻어진 기능성 고분자 비드.(d) Functional polymer beads obtained from toluene.

표 1 : 방사선 중합법에 의해 제조된 용매에 따른 기능성 고분자 비드의 특성Table 1: Properties of Functional Polymer Beads by Solvents Prepared by Radiation Polymerization

표 2 : 방사선 중합법에 의해 제조된 단량체 농도의 비에 따른 기능성 고분자 비드의 특성Table 2: Properties of Functional Polymer Beads with Ratio of Monomer Concentrations Prepared by Radiation Polymerization

표 3 : 방사선 중합법에 의해 제조 된 방사선 조사량에 따른 기능성 비드의 특성Table 3: Characteristics of functional beads according to the amount of radiation produced by the radiation polymerization method

본 발명은 여러 관능기를 갖은 비닐계 단량체를 일반적인 유기용매에 녹인 후, 방사선(전자선 및 감마선)을 조사하여 기능성 고분자 비드를 쉽게 제조할 수 있게 한 것이다.The present invention is to facilitate the production of functional polymer beads by dissolving a vinyl monomer having a plurality of functional groups in a general organic solvent, and then irradiated with radiation (electron beam and gamma ray).

이하, 본 발명의 바람직한 실시예를 좀 더 구체적으로 설명한다.Hereinafter, preferred embodiments of the present invention will be described in more detail.

(실시예 1)(Example 1)

방사선 중합법을 이용한 본 발명의 기능성 고분자 비드 제조에 있어서 비닐 계 단량체는 화학식 1과 같으며, 에폭시(epoxy)기를 갖은 단량체를 사용함으로써 관능기가 쉽게 도입되도록 고안하였다.In the production of the functional polymer beads of the present invention using a radiation polymerization method, the vinyl monomer is the same as that of Formula 1, and the functional group is designed to be easily introduced by using a monomer having an epoxy group.

먼저, 일반 유기용매에 혼합 단량체(GMA/DEGDMA=1/1, 몰비)를 용해시켜, 질소기류하에서 방사선 총량 30 kGy를 조사하였다. 방사선 조사 후, 흰색 분말상의 고분자가 얻어 지면, 그것을 필터하여 60℃에서 12시간 건조시킴으로써 기능성 고분자 비드를 얻을 수 있다. 표 1은 방사선 중합법에 의한 용매에 따른 기능성 고분자 비드의 특성을 나타내고 있다.First, the mixed monomer (GMA / DEGDMA = 1/1, molar ratio) was dissolved in the general organic solvent, and the total radiation amount of 30 kGy was irradiated under nitrogen stream. When a white powdery polymer is obtained after irradiation, functional polymer beads can be obtained by filtering it and drying at 60 ° C for 12 hours. Table 1 shows the characteristics of the functional polymer beads according to the solvent by the radiation polymerization method.

상기의 방법으로 얻어진 기능성 고분자 비드가 성공적으로 이루어진 것을 확인하기 위하여 SEM을 측정 분석하였다.SEM was measured and analyzed to confirm that the functional polymer beads obtained by the above method were successful.

도 1은 본 발명인 고기능성 고분자 비드의 SEM 분석 사진을 나타내고 있으며, 이 결과로서 고기능성 고분자 비드가 성공적으로 제조됨을 확인할 수 있었다.Figure 1 shows a SEM analysis of the high functional polymer beads of the present invention, as a result it was confirmed that the high functional polymer beads were successfully produced.

(실시예 2)(Example 2)

다양한 기능성 고분자 비드를 제조하기 위하여 실시예 1과 같은 방법으로 GMA와 DEGDMA의 몰비를 달리하여 제조된 방사선을 조사하였다. 표 2는 에탄올에서 GMA와 DEGDMA의 단량체비를 달리하며 기능성 고분자 재료의 특성을 나타내고 있다.In order to prepare a variety of functional polymer beads was irradiated with radiation prepared by varying the molar ratio of GMA and DEGDMA in the same manner as in Example 1. Table 2 shows the properties of the functional polymer material with different monomer ratios of GMA and DEGDMA in ethanol.

(실시예 3)(Example 3)

실시예 l과 같은 방법으로 단량체 몰비(GMA/DEGDMA =1/1)을 일정하게 하고 에탄올 용매에서 방사선 조사량을 달리하여 크기가 다른 기능성 고분자 비드를 얻을 수 있었다. 표 3은 에탄올에서 단량체 몰비(GMA/DEGBMA =1/1)을 일정하게 하고 방사선 조사량에 따른 기능성 고분자 비드의 특성을 나타내고 있다.In the same manner as in Example 1, the monomer molar ratio (GMA / DEGDMA = 1/1) was constant and the functional polymer beads having different sizes could be obtained by varying the radiation dose in the ethanol solvent. Table 3 shows the properties of the functional polymer beads in accordance with the irradiation amount of the monomer molar ratio (GMA / DEGBMA = 1/1) constant in ethanol.

(실시예 4)(Example 4)

실시예 1과 같은 방법으로 본 발명의 기능성 고분자 비드를 제조함에 있어서 비닐계 단량체는 화학식 2와 같으며, 클로라이드기 (chloride)를 갖은 단량체를 사용함으로써 관능기가 쉽게 도입되도록 고안하였다.In preparing the functional polymer beads of the present invention in the same manner as in Example 1, the vinyl monomer is the same as Formula 2, and the functional group is designed to be easily introduced by using a monomer having a chloride.

(실시예 5)(Example 5)

실시예 1과 같은 방법으로 본 발명의 기능성 고분자 비드를 제조함에 있어서 비닐계 단량체는 화학식 3과 같으며, 클로라이드기 (chloride)를 갖은 단량체를 사용함으로써 관능기가 쉽게 도입되도록 고안하였다.In preparing the functional polymer beads of the present invention in the same manner as in Example 1, the vinyl monomer is the same as Formula 3, and the functional group is designed to be easily introduced by using a monomer having a chloride.

이상과 같이 본 발명은 방사선을 사용함으로써 기능성 고분자 비드를 실온에서 쉽게 제조할 수 있는 효과가 있었다.As described above, the present invention has an effect of easily producing functional polymer beads at room temperature by using radiation.

또한, 다양한 관능기를 갖은 기능성 고분자 비드는 다양한 바이오 물질을 쉽게 고정화시키는 특성을 갖고 있어서, 새로운 기능성 바이오 재료뿐만 아니라 단백질 분리용 아피니티(affinity) 칼럼 재료로 이용할 수 있는 등의 많은 효과가 있었다.In addition, functional polymer beads having various functional groups have characteristics of easily immobilizing various biomaterials, and thus, there are many effects such as new functional biomaterials as well as affinity column materials for protein separation.

Claims (3)

관능기를 갖은 혼합 비닐계 단량체를 유기용매에 용해시켜 질소를 치환한 후 방사선을 조사하여 중합시킴으로써 기능성 고분자 비드를 생성시키고, 생성된 비드를 필터하여 닦고 건조시키는 방사선 중합법에 의한 고기능성 고분자 비드의 제조방법.The mixed vinyl monomer having a functional group was dissolved in an organic solvent to substitute nitrogen, and then irradiated with radiation to polymerize to produce functional polymer beads. Manufacturing method. 제 1항에 있어서, 혼합 비닐계 단량체는 Diethyleneglycol dimethacrylate (DEGDMA), Glycidyl methacrylate (GMA), Methacryloyl chloride (MA-C), Acryloyl chloride (AA-C) 중 적어도 하나임을 특징으로 하는 방사선 중합법에 의한 기능성 고분자 비드의 제조방법.The method of claim 1, wherein the mixed vinyl monomer is at least one of Diethyleneglycol dimethacrylate (DEGDMA), Glycidyl methacrylate (GMA), Methacryloyl chloride (MA-C), Acryloyl chloride (AA-C) Method for producing functional polymer beads. 관능기를 갖은 혼합 비닐계 단량체를 유기용매에 용해시켜 질소를 치환한 후 방사선을 조사하여 중합시킴으로써 기능성 고분자 비드를 생성시키고, 생성된 비드를 필터하여 닦고 건조시키는 방사선 중합법에 의한 고기능성 고분자 비드의 제조방법에 의해 제조된 방사선 중합법에 의한 기능성 고분자 비드.The mixed vinyl monomer having a functional group was dissolved in an organic solvent to substitute nitrogen, and then irradiated with radiation to polymerize to produce functional polymer beads. Functional polymer beads by radiation polymerization produced by the production method.
KR1020000081429A 2000-12-13 2000-12-13 Preparation Method of the Functional Polymeric Beads by Radiation-induced Polymerization and Its Functional Polymeric Beads KR20010016592A (en)

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KR20010078876A (en) * 2001-05-07 2001-08-22 이상진 Preparation Method of the Metal Particles with Nanometer Size Irradiated by Radiation and Its Metal Particle with Nanometer Size
US7939578B2 (en) 2007-02-23 2011-05-10 3M Innovative Properties Company Polymeric fibers and methods of making

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JPS56140256A (en) * 1980-04-03 1981-11-02 Japan Atom Energy Res Inst Fixed material of spherical polymer
US5126381A (en) * 1988-12-19 1992-06-30 Dow Corning Corporation Bead processor
JPH06248107A (en) * 1993-02-24 1994-09-06 Dainippon Ink & Chem Inc Production of porous bead
JPH11322997A (en) * 1998-05-14 1999-11-26 Dainippon Ink & Chem Inc Preparation of porous bead

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US3985632A (en) * 1974-01-17 1976-10-12 California Institute Of Technology Small, porous polyacrylate beads
JPS56140256A (en) * 1980-04-03 1981-11-02 Japan Atom Energy Res Inst Fixed material of spherical polymer
US5126381A (en) * 1988-12-19 1992-06-30 Dow Corning Corporation Bead processor
JPH06248107A (en) * 1993-02-24 1994-09-06 Dainippon Ink & Chem Inc Production of porous bead
JPH11322997A (en) * 1998-05-14 1999-11-26 Dainippon Ink & Chem Inc Preparation of porous bead

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010078876A (en) * 2001-05-07 2001-08-22 이상진 Preparation Method of the Metal Particles with Nanometer Size Irradiated by Radiation and Its Metal Particle with Nanometer Size
US7939578B2 (en) 2007-02-23 2011-05-10 3M Innovative Properties Company Polymeric fibers and methods of making

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